CN1384891A - Cermet inert anode for use in electrolytic production of metals - Google Patents

Abstract

A cermet inert anode for the electrolytic production of metals such as aluminum is disclosed. The inert anode comprises a ceramic phase of the formula NixFe2yMzO(3y+x+z)+/-delta, where M is at least one metal selected from Zn, Co, Al, Li, Cu, Ti, V, Cr, Zr, Nb, Ta, W, Mb, Hf and rare earths, preferably Zn and/or Co, x is from 0.1 to 0.99, y is from 0.0001 to 0.9, z is from 0.0001 to 0.5, and delta is from 0 to about 0.3. Preferred ceramic compositions comprise Fe2O3, NiO and ZnO or CoO. The cermet inert anode also comprises a metal phase such as Cu, Ag, Pd, Pt, Au, Rh, Ru, Ir and/or Os. A preferred metal phase comprises a Cu and Ag. The cermet inert anodes may be used in electrolytic reduction cells for the production of commercial purity aluminum as well as other metals.

Description

The cermet inert anode that is used for the electrolytic preparation of metal

The present invention relates to for example electrolytic preparation of aluminium of metal, more specifically, the present invention relates in electrolyzer, carry out electrolysis with the cermet inert anode that contains ceramic phase and metallographic phase.

Adopt the anode of inertia, non-consumable and dimensional stabilizing, can significantly reduce the energy of aluminium melting and improve fund efficient.Replace traditional carbon anode that the high design of electrolysis cells of productivity is utilized with inert anode, thereby reduce capital investment.But also obviously favourable to environment, because inert anode can not produce CO substantially ₂Or CF ₄Discharge.United States Patent (USP) 4374050 the transferee who transfers the application; 4374761; 4399008,4455211; 4582585; 4584172; 4620905; 5279715; Provide the example of some inert anode compositions in 5794112 and 5865980, be incorporated herein these patents as a reference.

It is anode material that the inert anode technology commercialization is run into a significant challenge.Since Hall-Heroult method in one's early years occurred, the researchist was seeking suitable inert anode material always.This anode material must satisfy some very difficult condition, for example, significantly reaction or obviously dissolving therein must not can take place with the sodium aluminum fluoride ionogen in described material, described material must not can in containing oxygen institute atmosphere with oxygen reaction or corrode, it is thermally-stabilised that described material should keep under about 1000 ℃ temperature, described material must compare cheap and should have excellent mechanical intensity, described material must be in the working temperature of fusion electrolysis groove, has high electroconductibility under for example about 900-1000 ℃, like this, the volts lost on the anode is very low.

Except mentioned above principle, the aluminium that adopts described inert anode to prepare should not be subjected to the remarkable pollution of anode material constituent element, though have been proposed in the past in the electrolysis of aluminum reducing bath and use inert anode, the use of this inert anode still is not put to business practice.A reason that lacks this practice is to adopt inert anode can not prepare the aluminium with technical grade purity for a long time, for example, in the aluminium of adopting known inert anode material preparation, has found Fe, and the foreign matter content of Cu and/or Ni is high as can't to accept.

Based on aforementioned introduction, and by discussing other deficiency of prior art, the present invention is developed.

The invention provides a kind of inert anode that contains ceramic phase and metallographic phase, the oxide compound of described ceramic phase preferred package iron content, nickel and at least a other metal such as zinc or cobalt, described metallographic phase preferably comprises at least a Cu of being selected from, Ag, Pd, Pt, Au, Rh, Ru, the metal of Ir and Os.

One aspect of the present invention provides a kind of cermet inert anode composition that is suitable for being used in the fusion electrolysis groove.It is Ni that said composition comprises at least a formula _xFe _2yM _zO _{(3y+x+z) ± δ}Ceramic phase, wherein, M is at least a Zn of being selected from, Co, Al, Li, Cu, Ti, V, Cr, Zr, Nb, Ta, W, Mb, the metal of Hf and rare earth, X are about 0.1-0.99, y is about 0.0001-0.9, the about 0.0001-0.5 of Z.The stoichiometry of oxygen can be passed through coefficient δ change, and the span of δ is 0-about 0.3.In the formula, can oxygen partly be substituted with F and/or N.Described cermet inert anode composition also comprises at least a metallographic phase, and preferred metallographic phase comprises Cu and/or Ag, but also can comprise at least a Pd of being selected from, Pt, Au, Rh, Ru, the inert metal of Ir and Os.

Another aspect of the present invention provides a kind of preparation cermet inert anode method for compositions, and this method comprises the steps: that with at least a metal and formula be Ni _xFe _2yM _zO _{(3y+x+z) ± δ}Stupalith mix, wherein, M is at least a Zn of being selected from, Co, Al, Li, Cu, Ti, V, Cr, Zr, Nb, Ta, W, Mb, the metal of Hf and rare earth, X are about 0.1-0.99, y is about 0.0001-0.9, the about 0.0001-0.5 of Z, δ are 0-about 0.3.Suppress the mixture that is obtained, and described mixture is carried out sintering.

Another aspect of the present invention provides a kind of electrolyzer that is used to prepare metal, and this groove comprises molten salt bath, negative electrode and the cermet inert anode of the present invention that contains ionogen and wait to collect the oxide compound of metal.

Another aspect of the present invention provides a kind of method of utilizing cermet inert anode of the present invention to prepare the aluminium of technical grade purity.

From following detailed, one of skill in the art will find other direction of the present invention and advantage.

Fig. 1 is the cut-away section synoptic diagram according to the electrolyzer of the cermet inert anode of one embodiment of the invention of comprising that is used to prepare aluminium.

Fig. 2 is a kind of ternary phase diagrams, is used for illustrating the scope at the oxide compound of the nickel that uses according to the inert anode compositions of one embodiment of the invention, iron and zinc.

Fig. 3 is a kind of ternary phase diagrams, is used for pointing out the amount at the oxide compound of the nickel, iron and the zinc that use according to the specific inert anode compositions of embodiment of the present invention.

Shown in Fig. 4 is that anode composition at the zinc oxide of the oxide compound of the oxide compound that will contain nickel, iron and various different quantitiess is exposed to after the salt bath solution of the electrolyzer that typically is used to prepare aluminium the weight percentage example of the dissolution of metals in this salt bath solution.

Shown in Fig. 5 and 6 is after the anode composition of the oxide compound of the zinc of the oxide compound of the oxide compound that will contain nickel, iron and different amts is exposed to the salts solution that typically is used for the electrolysis of aluminum reducing bath, the weight percentage example of the dissolved oxygen thing in this salt bath solution.

Fig. 7 forms different Ni-Fe-Zn-O anode material dissolved NiO in the aluminium reducing salt bath solution of standard, Fe ₂O ₃Equal-value map with ZnO.

Fig. 8 forms the different NiO solubleness equal-value map of Ni-Fe-Zn-O anode material in the aluminium reducing salt bath solution of standard.

Fig. 9 is the ternary phase diagrams of compositing range that is used for illustrating the oxide compound of this nickel that uses according to the inert anode compositions of another embodiment of the invention, iron and cobalt.

Figure 10 is the ternary phase diagrams that is used for illustrating at the oxide amount of the nickel, iron and the cobalt that use according to the concrete inert anode compositions of embodiment of the present invention.

Shown in Figure 11 is after the anode composition of the oxide compound of the cobalt of the oxide compound of the oxide compound that will contain nickel, iron and different amts is exposed to the salt bath solution that typically is used for the aluminium preparation vessel, the oxide compound percentage ratio example of dissolved iron, cobalt and the nickel in this salt bath solution.

Fig. 1 illustrative be used for aluminium preparation comprise electrolyzer according to the cermet inert anode of one embodiment of the invention, this electrolyzer comprises a crucible 10 that is positioned at protection crucible 20 inside.Sodium aluminum fluoride body lotion 30 is contained in the interior crucible 10, and negative electrode 40 is in the electrolytic solution 30, and cermet inert anode 50 is arranged in body lotion 30.Aluminum oxide transfer lime 60 parts enter the crucible 10 that is positioned at body lotion 30 tops, and negative electrode 40 and inert anode 50 separate for gap 70, and this gap is called anode-negative electrode gap (ACD).The aluminium 80 of on period preparation is deposited on the negative electrode 40 and the bottom of crucible 10, and except preparation aluminium, cermet inert anode of the present invention also can be used for by the oxide compound of electrolytic reduction metal or other salt.Prepare other metal, for example lead, magnesium, zinc, zirconium, titanium, lithium, calcium, silicon, barium, strontium, scandium, niobium, vanadium, tantalum, tin, germanium, indium, hafnium, molybdenum etc.

The term of Shi Yonging " inert anode " refers at aluminum and is equipped with the non-consumble basically anode that has gratifying erosion resistance and stability in the process herein.Comprise cermet material of the present invention to the described inert anode of small part, for example, described inert anode can all be made by cermet material of the present invention, perhaps, described inert anode can comprise an outer coat or the thin layer made by described cermet material that is positioned on the central core part.When described sintering metal as outside during coat, preferably its thickness is 0.1-50mm, more preferably 1 to 10 or 20mm.

The term of Shi Yonging " aluminium of technical grade purity " refers to the aluminium that satisfies commercial purity rubric when adopting electrolytic reduction to prepare herein.Adopt the aluminium of the technical grade purity of cermet inert anode preparation of the present invention preferably to contain maximum 0.2 weight %Fe, 0.1 weight %Cu and 0.03 weight %Ni.In a more preferred embodiment, the aluminium of described technical grade purity contains maximum 0.15 weight %Fe, 0.034 weight %Cu and 0.03 weight %Ni.In particularly preferred embodiments, the aluminium of described technical grade purity contains maximum 0.13 weight %Fe, 0.03 weight %Cu and 0.03 weight %Ni.Other impurity in the aluminium of described technical grade purity also preferably satisfies following weight percentage ratio standard: maximum 0.2 Si, maximum 0.03 Zn and maximum 0.034 Co more preferably make Zn and Co foreign matter content be lower than 0.03 weight % respectively.More preferably make the Si foreign matter content be lower than 0.15 or 0.10 weight %.

Inert anode compositions of the present invention typically comprises at least a ceramic phase of about 1-99.9 weight % and at least a metallographic phase of about 0.1-99 weight %.Described ceramic phase preferably accounts for the described cermet material of about 50-95 weight %, and described metallographic phase preferably accounts for the described sintering metal of about 5-50 weight %.More preferably, described ceramic phase accounts for the described sintering metal of about 80-90 weight %, and described metallographic phase accounts for the described sintering metal of about 10-20 weight %.Attention: for each digital scope that herein proposes or boundary, all numerals in described scope or boundary are included between the minimum declared and the maximum value and are each mark or decimal, can think by this descriptions appointment and disclosed.

But the oxide compound of preferred iron content of described ceramic phase and nickel, and at least a additional oxide, for example oxide compound of the oxide compound of zinc and/or cobalt.The molecular formula of described ceramic phase is preferably Ni _xFe _2yM _zO _{(3y+x+z) ± δ}Ceramic phase, wherein, M is at least a Zn of being selected from, Co, Al, Li, Cu, Ti, V, Cr, Zr, Nb, Ta, W, Mb, the metal of Hf and rare earth, preferred Zn and/or Co, X is about 0.1-0.99, the about 0.0001-0.9 of y, the about 0.0001-0.5 of Z.In aforementioned molecular formula, the stoichiometry of oxygen needs not be equal to 3Y+X+Z, but can slightly be increased or be reduced by coefficient δ according to for example roasting condition, and the δ value can be about 0.3 for 0-, preferred 0-about 0.2.

In a preferred embodiment, described ceramic phase comprises the oxide compound of iron, nickel and zinc, and in this embodiment, described ceramic phase comprises the oxide compound of nickel, iron and zinc, and its molecular formula is Ni _xFe _2yM _zO _{(3y+x+z) ± δ}, wherein, X is the molar fraction of NiO, y is Fe ₂O ₃Molar fraction, Z is the molar fraction of ZnO.

In this embodiment, the molar fraction of NiO typically is about 0.2-0.99, Fe ₂O ₃Molar fraction typically be about 0.0001-0.8, the molar fraction of ZnO typically is about 0.0001-0.3, in a kind of preferred composition, the molar fraction of NiO is about 0.45-0.8, Fe ₂O ₃Molar fraction be about 0.05-0.499, the molar fraction of ZnO is about 0.001-0.26, in a kind of preferred composition, the molar fraction of NiO is about 0.45-0.65, Fe ₂O ₃Molar fraction be about 0.2-0.49, the molar fraction of ZnO is about 0.001-0.22.

Table 1 has been listed NiO, Fe ₂O ₃With the typical case of ZnO, preferably with preferred molar fraction, listed molar fraction can be multiply by 100 and represent its molecular fraction, in described scope, the solubleness of each oxide compound constituent element in electrolyte solution significantly descends, and can think that the solubleness of oxide compound in electrolyte solution improves the purity of the aluminium prepare than low energy in this solution.

Table 1

NiO, Fe ₂O ₃Molar fraction with ZnO

	????NiO	????Fe 2O 3	????ZnO
				The typical case	0.2-0.99	?0.0001-0.8	?0.0001-0.3
Preferably	0.45-0.8	?0.05-0.499	?0.001-0.26
				More preferably	0.45-0.65	?0.2-0.49	?0.001-0.22

Fig. 2 is used to the NiO that illustrates that preparation is used according to the inert anode compositions of this embodiment of the present invention, Fe ₂O ₃With the raw-material typical case of ZnO, the preferably and more preferably ternary phase diagrams of scope.Though the molecular fraction shown in Fig. 2 is based on material N iO, Fe ₂O ₃And ZnO, but the oxide compound of other nickel, iron and zinc, the compound that can form oxide compound when perhaps calcining can be used as starting material.

Table 2 has been listed some ternary Ni-Fe-Zn-O materials of the ceramic phase that may be suitable as cermet inert anode of the present invention, and some control materials.Except the phase of listing in the table 2, can there be other a small amount of or micro-phase.

Table 2

The Ni-Fe-Zn-O composition

The sample code name	Name is formed	The element wt percentage ratio Fe that measures, Ni, Zn	Structure type (adopting XRD to determine)
				????5412	????NiFe 2O 4	????48，23.0，0.15	????NiFe 2O 4
????5324	????NiFe 2O 4+NiO	????34，36，0.06	????NiFe 2O 4，NiO
				????E4	????Zn 0.05Ni 0.95Fe 2O 4	????43，22，1.4	????NiFe 2O 4
????E3	????Zn 0.1Ni 0.9Fe 2O 4	????43，20，2.7	????NiFe 2O 4
				????E2	????Zn 0.25Ni 0.75Fe 2O 4	????40，15，5.9	????NiFe 2O 4
????E1	????Zn 0.25Ni 0.75Fe 1.9O 4	????45，18，7.8	????NiFe 2O 4
				????E	????Zn 0.5N 0.5Fe 2O 4	????45，12，13	????(ZnNi)Fe 2O 4，ZnO S
????F	????ZnFe 2O 4	????43，0.03，24	????ZnFe 2O 4，ZnO
				????H	????Zn 0.5NiFe 1.5O 4	????33，23，13	????(ZnNi)Fe 2O 4，NiO S
????J	????Zn 0.5Ni 1.5FeO 4	????26，39，10	????NiFe 2O 4，NiO
				????L	????ZnNiFeO 4	????22，23，27	????(ZnNi)Fe 2O 4，NiO S，ZnO
????ZD6	????Zn 0.05Ni 1.05Fe 1.9O 4	????40，24，1.3	????NiFe 2O 4
				????ZD5	????Zn 0.1Ni 1.1Fe 1.8O 4	????29，18，2.3	????NiFe 2O 4
????ZD3	????Zn 0.12Ni 0.94Fe 1.88O 4	????43，23，3.2	????NiFe 2O 4
				????ZD1	????Zn 0.5Ni 0.75Fe 1.5O 4	????40，20，11	????(ZnNi)Fe 2O 4
????DH	????Zn 0.18Ni 0.96Fe 1.8O 4	????42，23，4.9	????NiFe 2O 4，NiO
				????DI	????Zn 0.08Ni 1.17Fe 1.5O 4	????38，30，2.4	????NiFe 2O 4，NiO
????DJ	????Zn 0.17Ni 1.1Fe 1.5O 4	????36，29，4.8	????NiFe 2O 4，NiO
				????BC2	????Zn 0.33Ni 0.67O	????0.11，52，25	????NiO S

S refers to the skew peak

Fig. 3 is used for the used material N iO of composition that illustrates that preparation table 2 is listed, Fe ₂O ₃With the ternary phase diagrams of the amount of ZnO, described composition can be as the ceramic phase of cermet inert anode, and this inert anode can be used for preparing the aluminium according to technical grade purity of the present invention then.

Table 2 is listed and Ni-Fe-Zn-O composition shown in Figure 3 can have been adopted following step and is prepared and tests.Oxide powder can adopt wet method method or traditional commercial run to synthesize.Starting compound comprises Ni, Fe, and a kind of in the oxide compound of Zn, muriate, acetate, nitrate, tartrate, Citrate trianion and the vitriol or their mixture, these precursors can be buied by supplier such as Aldrich and Fisher place.The chemical that requires quantity is dissolved in the deionized water can prepares homogeneous solution.By adding ammonium hydroxide and stirring the pH value of solution value is adjusted to 6-9, preferred pH value is 7-8, adopt baking oven, lyophilizer, spray-dryers etc. are with described viscous soln drying, the drying solid that is obtained is a unformed shape, in for example 600-800 ℃ temperature the drying solid calcining can be obtained the crystalline oxide powder in 2 hours.Then, the oxide powder single shaft such as is pressed at static pressure is pressed into garden sheet form, pressing pressure is 10000-30000Psi, typically is 20000Psi.In air, the garden sheet of being suppressed is carried out sintering, sintering temperature is 1000-1500 ℃, typically be 1200 ℃, time is 2-4 hour, and the crystalline structure of the oxide compound garden sheet behind the sintering and composition can adopt plasma (ICP) technology of X-ray diffraction 2 θ (XRD) and jigger coupling to analyze.

Solubleness to Ni-Fe-Zn-O ceramic phase composition is measured, by under 960 ℃, the solubleness that the sintered oxide garden sheet of about 3g is kept measuring in 96 hours every kind of ceramic mixture in the standard sodium aluminum fluoride melting salt body lotion of 160g, described standard salt body lotion is contained in the platinum crucible and passes through NaF, AlF, Greenland sodium aluminum fluoride, CaF ₂And Al ₂O ₃Prepare, make NaF:AlF ₃=1.1, Al ₂O ₃=5 weight %, CaF ₂=5 weight % are prepared from.In described these tests, dry air is with 100cm ³/ minute low flow velocity above saline solution, circulate and periodically carry out in the fusion saline solution to keep the oxidisability condition with bubbling, periodically taking out the melt sample carries out chemical body lotion analysis.

Fig. 4 shows the Fe of the composition E3 that periodically records, the foreign matter content of Zn and Ni.After 50 hours, the solubleness of Fe is 0.075 weight %, and it converts Fe to ₂O ₃Solubleness be 0.1065 weight %.The solubleness of Zn is 0.008 weight %, and its corresponding ZnO solubleness is 0.010 weight %, and the solubleness of Ni is 0.004 weight %, and its solubleness that converts NiO to is 0.005 weight %.

When adopting aforesaid solubleness measuring method, the weight percent of total dissolved oxygen thing preferably is lower than 0.1 weight %, and more preferably less than 0.08 weight %, total dissolved oxygen thing that will adopt abovementioned steps to record herein is Fe ₂O ₃, the amount of NiO and ZnO is defined as " Hall groove body lotion solubleness ".The Hall groove electrolytic solution solubleness of this composition preferably is lower than the solubleness of the nickel ferrite based magnetic loaded with stoichiometric composition.

Table 3 has been listed the name of every kind of ceramic phase sample being tested and has been formed the weight in average per-cent of dissolution of metals in the electrolytic solution (Fe, Ni and Zn), and dissolved oxide compound (Fe in the electrolytic solution ₂O ₃, NiO and ZnO) weight in average per-cent.After oxide compound sample constituent element has reached capacity, determine the content of described dissolution of metals and oxide compound in electrolytic solution is formed.This result also is expressed as the saturation value of oxide compound in the electrolytic solution.Total dissolved oxygen thing content is the saturated content sum of each oxide compound in the electrolytic solution, and it is lower to it is desirable to total dissolved oxygen thing content.

Table 3

Ceramic phase solubleness in 960 ℃ standard salt body lotion

Name is formed	The sample code name	The weight in average percentage ratio of dissolution of metals			The weight in average percentage ratio of dissolved oxygen thing
									????Fe	????Ni	????Zn	????Fe 2O 3	????NiO	????ZnO	??Total
		??NiO	????X	????0.014 *	????0.032	????＜0.004 *	????0.020 *	????0.041								????0.006 *	??0.068
??Fe 2O 3	????Z								????0.097	????na	????na	????0.139	????0.003 *	????0.006 *	??0.148
		??NiFe 2O 4	????5412(D)	????0.052	????0.009	????0.004	????0.074	????0.011								????0.005 *	??0.090
??NiFe 2O 4+NiO	????5324								????0.033	????0.018	????＜0.004 *	????0.047	????0.023	????0.006 *	??0.076
		??ZnO	????Y	????na	????na	????0.082	????0.020 *	????0.003 *								????0.102	??0.125
??ZnO	????Y								????na	????na	????0.085	????0.020 *	????0.003 *	????0.106	??0.129
		??ZnFe 2O 4	????F	????0.075	????na	????0.039	????0.107	????0.003 *								????0.049	??0.159
??ZnFe 2O 4	????F								????0.087	????＜0.001 *	????0.052	????0.124	????＜0.001	????0.065	??0.190
		??Ni 0.67Zn 0.33O	????BC2	????na	????0.033	????0.053	????0.020 *	????0.042								????0.066	??0.128
??Ni 0.67Zn 0.33O	????BC2								????na	????0.011	????0.056	????0.020 *	????0.014	????0.070	??0.104
		??Ni 0.5Zn 0.5Fe 2O 4	????E	????0.086	????0.002	????0.031	????0.123	????0.003								????0.038	??0.164
??Ni 0.75Zn 0.25Fe 1.90O 4	????E1								????0.086	????0.005	????0.022	????0.123	????0.006	????0.027	??0.156
		??Ni 0.75Zn 0.25Fe 2O 4	????E2	????0.082	????0.004	????0.018	????0.117	????0.005								????0.022	??0.144
??Ni 0.90Zn 0.10Fe 2O 4	????E3								????0.075	????0.004	????0.008	????0.107	????0.005	????0.010	??0.122
		??Ni 0.95Zn 0.05Fe 2O 4	????34	????0.070	????0.004	????0.005	????0.100	????0.006								????0.006	??0.112
??NiZnFeO 4	????L								????0.006	????0.004	????0.102	????0.009	????0.005	????0.127	??0.141

Name is formed	The sample code name	The weight in average percentage ratio of dissolution of metals			The weight in average percentage ratio of dissolved oxygen thing
									????Fe	????Ni	????Zn	????Fe 2O 3	????NiO	????ZnO	??Total
		??NiZn 0.5Fe 1.5O 4	????H	????0.018	????0.011	????0.052	????0.026	????0.014								????0.065	??0.105
??Ni 1.5Zn 0.5FeO 4	????J								????0.011	????0.007	????0.029	????0.016	????0.009	????0.036	??0.061
		??Ni 1.05Zn 0.05Fe 1.9O 4	????ZD6	????0.049	????0.004	????0.008	????0.070	????0.004								????0.008	??0.085
??NiFe 1.5O 4+5％ZnO	????-								????0.054	????0.005	????0.014	????0.077 **	????0.006	????0.017 **	??0.100
		??Ni 0.95Zn 0.12Fe 1.9O 4	????-	????0.034	????0.008	????0.014	????0.049	????0.010								????0.018	??0.077
??Ni 0.94Zn 0.12Fe 1.88O 4	????ZD3								????0.062 **	????0.005	????0.010	????0.089 **	????0.006	????0.012	??＞0.107
		??Ni 0.94Zn 0.12Fe 1.88O 4	????ZD3	????0.044 **	????0.005	????0.019	????0.063 **	????0.006								????0.024	??＞0.093
??Ni 1.17Zn 0.08Fe 1.50O 4	????D1								????0.019	????0.012	????0.009	????0.027	????0.015	????0.011	??0.053
		??Ni 0.75Zn 0.50Fe 1.50O 4	????ZD1	????0.052	????0.065	????0.042	????0.074	????0.008								????0.052	??0.134
??Ni 0.10Zn 0.17Fe 1.50O 4	????DJ								????0.024	????0.004	????0.014	????0.034	????0.005	????0.017	??0.056
		??Ni 0.96Zn 0.17Fe 1.50O 4	????DH	????0.044	????0.007	????0.022	????0.063	????0.009								????0.027	??0.099
??Ni 1.10Zn 0.10Fe 1.80O 4	????ZD5								????0.039	????0.006	????0.012	????0.056	????0.0076	????0.015	??0.079

Remarks: na=does not analyze, ^*Finger is carried on the back under the end content at salt, ^*Refer to not reach capacity after 96 hours

Fig. 5 and Fig. 6 show the NiO that contains different amts, Fe with curve form ₂O ₃With the amount of the dissolved oxygen thing of the sample of ZnO, the composition shown in Fig. 5 shows low-down oxide dissolution degree, and the composition of ZnO that particularly contains 1-30% (mole) is all the more so.Oxide dissolution degree when the oxide concentration of zinc is 5-25% (mole) is extremely low.Composition shown in Fig. 5 descends along the line of being ordered to D by the BC2 point in Fig. 3.Composition shown in Fig. 6 is compared with the composition among Fig. 5 has higher oxide dissolution degree, and the composition among Fig. 6 is descended by the spinel line that the F point is ordered to D in Fig. 3.As shown in Figure 6, different with the composition that descends along the BC2-D line, the oxide dissolution degree of the composition of D-F line does not have mnm..When oxide compound is formed Ni Fe ₂O ₄Become Zn Fe ₂O ₄The time, dissolved oxygen thing content total in the body lotion increases.Improved oxide composition of the present invention has been shown in the composition district of Fig. 2, and it has obviously lower electrolyte dissolution degree.

Adopt business software (JMP) to simulate the equal-value map of the solubility results that table 3 lists, Fig. 7 is the NiO that contains different amts, Fe ₂O ₃Total dissolved oxygen thing (NiO, Fe with the ZnO ceramic composition ₂O ₃And ZnO) equal-value map.Figure 7 illustrates the zone that total dissolved oxygen thing content is lower than 0.10 weight %, and total dissolved oxygen thing content is lower than the zone of 0.075 weight %.

Fig. 8 is the NiO that contains different amounts, Fe ₂O ₃Equal-value map with the dissolving NiO of the ceramic phase composition of ZnO, by the lower right corner of Fig. 8 as can be seen, be rich in the maximum dissolving NiO of ceramic combination deposits yields of NiO, for example, dissolving NiO content has been shown among Fig. 8 has been higher than 0.025 respectively, 0.030,0.035 and the zone of 0.040 (weight percent), this high-load dissolving NiO is unfavorable especially in the preparation of the aluminium of technical grade purity, because the standard of technical grade purity has been made very strict regulation to the MAD of nickel impurity, for example, the high-content of Ni is 0.03 or 0.34 weight percent.The combined thing of preferably ceramic of the present invention not only has total oxide dissolution degree of obvious reduction, but also has the NiO solubleness that obviously reduces.

In another embodiment of the invention, the ceramic phase in the described cermet material comprises the oxide compound of iron, nickel and cobalt.In this embodiment, described ceramic phase preferred package is nickeliferous, the oxide compound of iron and cobalt, and its molecular formula is Ni _xFe _2yCo _zO _{(3y+x+z) ± δ}In the aforementioned molecular formula, the stoichiometric composition of oxygen needs not be equal to 3y+x+z, but can increase a little by coefficient δ or reduce according to roasting condition, and δ value span is that 0-is about 0.3, preferred 0-about 0.2.

In this embodiment, the molar fraction of NiO typically is about 0.15-0.99, Fe ₂O ₃Molar fraction typically be 0.0001-0.85, the molar fraction of CoO typically is 0.0001-0.45, in preferred a composition, the molar fraction of NiO is about 0.15-0.6, Fe ₂O ₃Molar fraction be about 0.4-0.6, the molar fraction of CoO is about 0.001-0.25.In preferred composition, the molar fraction of NiO is about 0.25-0.55, Fe ₂O ₃Molar fraction be about 0.45-0.55, the molar fraction of CoO is about 0.001-0.2.Table 4 has been listed NiO, Fe ₂O ₃With the typical case of CoO, preferably with preferred molar fraction scope, the molar fraction of listing can be multiply by 100 and represent its molecular fraction.In described scope, the solubleness of respectively forming oxide compound in the electrolyte solution significantly descends, and can think that the oxide dissolution degree improves the purity of the aluminium for preparing than low energy in described solution.

Table 4

NiO, Fe ₂O ₃Molar fraction with CoO

	????NiO	????Fe 2O 3	????CoO
				The typical case	0.15-0.99	?0.0001-0.85	?0.0001-0.45
Preferably	0.15-0.6	?0.4-0.6	?0.001-0.25
				More preferably	0.25-0.55	?0.45-0.55	?0.001-0.2

Fig. 9 is used to illustrate the NiO of preparation according to the inert anode compositions use of this embodiment of the present invention, Fe ₂O ₃With the typical case of CoO raw material, preferably with the ternary phase diagrams of preferred scope.Though the molecular fraction shown in Fig. 9 is based on NiO, Fe ₂O ₃With the CoO raw material, still, the oxide compound of other iron, nickel and cobalt, the compound that can form oxide compound when perhaps calcining can be used as raw material.

Table 5 has been listed some Ni-Fe-Co-O materials of the ceramic phase that can be suitable as cermet inert anode of the present invention, and Co-Fe-O and Ni-Fe-O control material.Except each phase of listing in the table 5, can also there be other a small amount of or micro-phase.

Table 5

The Ni-Fe-Co-O composition

The sample code name	Name is formed	The element wt percentage ratio Fe that records, Ni, Co	Structure type (adopting XRD to determine)
				??CF	????CoFe 2O 4	????44，0.17，24	????CoFe 2O 4
??NCF1	????Ni 0.5Co 0.5Fe 2O 4	????44，12，11	????NiFe 2O 4
				??NCF2	????Ni 0.7Co 0.3Fe 2O 4	????45，16，7.6	????NiFe 2O 4
??NCF3	????Ni 0.7Co 0.3Fe 1.95O 4	????42，18，6.9	????NiFe 2O 4
				??NCF4	????Ni 0.85Co 0.15Fe 1.95O 4	????44，20，3.4	????NiFe 2O 4
??NCF5	????Ni 0.80Co 0.3Fe 1.9O 4	????45，20，7.0	????NiFe 2O 4，NiO
				??NF	????NiFe 2O 4	????48，23，0	????N/A

Figure 10 is used to illustrate that preparation lists in the used NiO of composition of table 2, Fe ₂O ₃With the ternary phase diagrams of the amount of CoO raw material, described composition can be as the ceramic phase of described cermet inert anode, and this inert anode can be used to prepare the aluminium according to technical grade purity of the present invention then.

Sintered oxide garden sheet by will about 3g keeps measuring in 96 hours the solubleness of described Ni-Fe-Co-O ceramic phase composition in the standard sodium aluminum fluoride melting salt body lotion of 160g under 960 ℃.Described standard salt body lotion is contained in the platinum crucible, and passes through to NaF AlF ₃, Greenland sodium aluminum fluoride, CaF ₂And Al ₂O ₃Prepare, make NaF: AlF ₃=1.1, Al ₂O ₃=5 weight %, CaF ₂=5 weight % are prepared from.Dry air is with 100cm ³The low flow velocity of/min circulates above described salt bath solution, and periodically bubbling enters in the fused salt to keep the oxidisability condition, and periodically taking out described melt sample carries out chemical analysis.When using aforesaid solubility test method, the weight percentage of total dissolved oxygen thing preferably is lower than 0.1 weight %, more preferably less than 0.08 weight %, and the Hall groove electrolytic solution solubleness that adopts preceding method to record, that is, and total dissolved oxygen thing Fe ₂O ₃, NiO and Co ₃O ₄Amount preferably be lower than the solubleness of nickel ferrite based magnetic loaded (nickel ferrite) with stoichiometric composition.

Table 6 has been listed the Hall groove electrolytic solution solubleness of Ni-Fe-Co-O ceramic phase material of the present invention, and as a comparison, the solubleness of nickel ferrite based magnetic loaded and cobalt ferrite composition also provides in table, and the solubility results that table 6 is listed is to record after body lotion is saturated.Total dissolved oxygen thing content in every kind of electrolytic solution is each oxide compound saturation solubility sum, and total dissolved oxygen thing content is low ideal.

Table 6

The oxide dissolution degree

		Saturation value in the electrolytic solution (weight %)
						The sample code name	Name is formed	??Nio	??Fe 2O 3	??Co 3O 4	??Total
??CF	????CoFe 2O 4	??0.003	??0.110	??0.055	??0.168
						??NCF1	????Ni 0.5Co 0.5Fe 2O 4	??0.005	??0.089	??0.026	??0.120
??NCF3	????Ni 0.7Co 0.3Fe 1.95O 4	??0.006	??0.040	??0.007	??0.053
						??NCF4	????Ni 0.85Co 0.15Fe 1.95O 4	??0.011	??0.056	??0.006	??0.073
??NCF5	????Ni 0.8Co 0.3Fe 1.9O 4	??0.006	??0.086	??0.017	??0.109
						??NF	????NiFe 2O 4	??0.011	??0.074	??＜0.001	??0.085
??NF	????NiFe 2O 4	??0.010	??0.090	??＜0.001	??0.10

Figure 11 shows the Fe that lists in table 6, the solubleness of Co and Ni oxide compound, table 6 is listed and ceramic phase compositions table of the present invention shown in Figure 11 again reveals low-down oxide dissolution degree, particularly for composition NCF4, all the more so, they have the Hall groove electrolytic solution solubleness that total dissolved oxygen thing is lower than 0.08 weight %.

Except the ceramic phase material of ubi supra, cermet inert anode of the present invention comprises at least a metallographic phase, and this metallographic phase can be a successive or discontinuous, swallow and, preferably comprise a kind of matrix metal and at least a inert metal.When described metallographic phase continuous distribution, it forms a kind of interconnected net or framework, thereby can significantly improve sintering metal anodic electroconductibility, when metallographic phase is discontinuous, dispersive metallics to small part is surrounded by ceramic phase, thereby can improve sintering metal anodic erosion resistance.

Copper and silver are preferred metallographic phase matrix metals.Yet, can adopt optional all or part of copper or the silver of substituting of other metal.In addition, additional metal is Co for example, Ni, and Fe, Al, Sn, Nb, Ta, Cr, Mo, W etc. can carry out alloying with the matrix metal of metallographic phase.The form that provides of this matrix metal can be the single powder of described metal or the powder of alloying, or the oxide compound of this metal or other compound, as CuO, and Cu ₂O etc.

The inert metal of described metallographic phase preferably comprises at least a Ag of being selected from, Pd, and Pt, Au, Rh, Ru, the metal of Ir and Os, more preferably described inert metal comprises Ag, Pd, Pt, Au and/or Rh.Most preferably described inert metal comprises Ag, Pd or their mixture.The form that provides of described inert metal can be the single powder of described metal or the powder of alloying, or the oxide compound of this metalloid or other compound, Yin oxide compound for example, the oxide compound of palladium etc.

In a preferred embodiment, described metallographic phase typically comprises the matrix metal of about 50-99.99 weight % and the inert metal of about 0.01-50 weight %, preferred described metallographic phase comprises the matrix metal of about 70-99.95 weight % and the inert metal of about 0.05-30 weight %, and most preferably described metallographic phase comprises the matrix metal of about 90-99.9 weight % and the inert metal of about 0.1-10 weight %.

The matrix metal that contains in the metallographic phase to inert anode and the type of inert metal and quantity are selected, to prevent that basically inert anode from undesirable corrosion taking place, dissolving or reaction, and make inert anode can bear it between the electrolytic etching of metal reduction period, to be subjected to high temperature action.For example, in the electrolytic preparation of aluminium, electrolyzer is typically at the lasting smelting temperature that is higher than 800 ℃, usually under 900-980 ℃ temperature, work, therefore, the fusing point of the metallographic phase in the inert anode that uses in this electrolyzer preferably is higher than 800 ℃, more preferably is higher than 900 ℃, and the best is to be higher than about 1000 ℃.

In one embodiment of the invention, described anodic metallographic phase comprise copper as matrix metal and more a spot of silver as inert metal, in this embodiment, preferred silver content is lower than about 10 weight % or 15 weight %.For example, silver content can be about 0.2-9 weight %, perhaps can be about 0.5-8 weight %, the rest is copper.By this more a spot of silver and this more copper are made up, can significantly improve the fusing point of Cu-Ag alloy, for example, the fusing point that comprises the alloy of 95 weight %Cu and 5 weight %Ag is about 1000 ℃, and the alloy that comprises 90 weight %Cu and 10 weight %Ag forms a kind of eutectic phase, about 780 ℃ of its fusing point.When described alloy was used as inert anode in the reduction cell at aluminium a part of, the electrolyzer typical case worked being higher than under 800 ℃ the smelting temperature, and therefore, this species diversity on the fusing point is meaningful especially.

In another embodiment of the invention, described metallographic phase comprise copper as matrix metal and more a spot of palladium as inert metal, in this embodiment, preferred Pd content is lower than about 20 weight %, more preferably about 0.1-10 weight %.

In yet another embodiment of the present invention, described metallographic phase comprise silver as matrix metal and more a spot of palladium as inert metal, in this embodiment, Pd content preferably is lower than about 50 weight %, more preferably about 0.05-30 weight %, and optimum content is about 0.1-20 weight %, and on the other hand, silver can be used alone as the anodic metallographic phase.

In another embodiment of the present invention, described anodic metallographic phase comprises Cu, Ag and Pd are in this embodiment, preferably to Cu, the amount of Ag and Pd is selected, so that make the fusing point that obtains alloy be higher than 800 ℃, more preferably be higher than 900 ℃, and preferably be higher than about 1000 ℃, silver content is preferably about 0.5-30 weight % of metallographic phase, and Pd content is preferably about 0.01-10 weight %.More preferably, silver content is about the 1-20 weight % of metallographic phase, and Pd content is about 0.1-10 weight %.Ag and Pd weight ratio are preferably about 2: 1-100: 1, more preferably about 5: 1-20: 1.

According to one embodiment of the invention, the matrix metal that contains in the described metallographic phase and the type and the quantity of inert metal are selected, so that the material that is obtained forms the alloy phase that at least a its fusing point is higher than the eutectic melting point of particular alloy system.For example, as the discussion that the front is carried out binary Cu-Ag alloy system, can control the addition of Ag, so that fusing point is significantly higher than the eutectic melting point of Cu-Ag alloy.The inert metal of other controlled amounts such as Pd etc. can be added in the Cu-Ag binary alloy system, to obtain the alloy that its fusing point is higher than this alloy system eutectic melting point.Therefore, can prepare binary according to the present invention, ternary, quad alloy etc., described alloy has sufficiently high fusing point for for the part of the cermet inert anode in the electrolytic etching of metal preparation vessel.

Cermet inert anode of the present invention can adopt for example powder sintered, sol-gel process, and technology such as slurry casting and spray up n. are come moulding in addition.Preferably, described inert anode adopts the powder compression and the moulding of agglomerating powder technology that will comprise oxide compound and metal.Inert anode can comprise the integral unit of this material.On the other hand, inert anode can comprise and have at least one coat made by cermet material of the present invention or the matrix of outer thin layer, perhaps can comprise one and be coated with the cermet material core of the present invention with different materials of forming, the described different materials of forming for example are a kind of potteries that does not comprise metallographic phase or comprise the decrement metallographic phase.

Before ceramic powder and metal-powder is compound, can adopt mixing tank with ceramic powder, for example commercially available NiO, Fe ₂O ₃Mixed with ZnO or CoO powder.Randomly, mixed ceramic powder can be ground to smaller szie.Afterwards, send in the calcining furnace, for example calcined 12 hours down at 1250 ℃.This calcining can obtain by for example Fig. 2, the mixture that the oxide compound shown in 3,9 and 10 constitutes.If desired, described mixture can comprise for example Cr of other oxide powder ₂O ₃Perhaps can form the metal such as the Al of oxide compound.

Described oxide mixture can be delivered in the ball mill, average particulate size is ground to about 10 μ m.Described tiny oxide particle is mixed in spray-dryer with polymeric binder and water, to make slurries.Described slurries contain for example about 60 weight % solids and about 40 weight % water, slurries are carried out spraying drying can produce exsiccant oxide agglomerate body, described coacervate can be delivered to the V-type mixing tank and mix with metal-powder.Perhaps, oxide compound and metal component spraying drying together.Described metal-powder can comprise pure basically metal and their alloy, perhaps can comprise the oxide compound of matrix metal and/or inert metal.

In a preferred embodiment, organic polymer binding agent that will about 0.1-10 part (weight), softening agent and dispersion agent are added in the pottery and metallics of 100 parts (weight), some suitable binding agents comprise polyvinyl alcohol, acrylate copolymer, polyglycol, polyvinyl acetate, polyisobutene, polycarbonate, polystyrene, polyacrylate, and their mixture and multipolymer.Binding agent that preferably will about 0.3-6 part (weight) adds in the pottery and metal mixture of 100 parts (weight).

Mixed pottery and metal powder mixture can be delivered to press, for example make anode shape at the inferior static pressure of the pressure of 10000-40000psi.The pressure of about 20000psi is all suitable especially for many occasions, can carry out sintering to the profiled member after the compacting in the controlled atmosphere generator of logical argon gas-oxygen mixture, nitrogen-oxygen mixture or other suitable mixture.The sintering temperature that is fit to may be 1000-1400 ℃.Described sintering oven was typically worked 2-4 hour down at 1350-1385 ℃.This sintering process can all be burnt all polymeric binder in the anode formed body.

The gas that provides during sintering preferably contains the oxygen of the 5-3000ppm that has an appointment, more preferably from about 5-700ppm, most preferably from about 10-350ppm.Oxygen concn is low can to cause metallographic phase content in the product than required value height, and too much oxygen can cause the phase (ceramic phase) that has too much containing metal oxide compound in the product, and the remaining part of described atmosphere preferably contains gas such as the argon gas that does not react with metal under temperature of reaction.

The sintered anode composition typically can be reduced to porosity acceptable level and can be avoided metallographic phase to ooze out in the atmosphere with controlled oxygen content.Described atmosphere can contain the oxygen of the controlled amounts of 17-350ppm based on argon gas.Anode can be in the tube furnace under 1350 ℃ sintering 2 hours, when anode composition was containing in the argon gas of oxygen of 70-150ppm sintering, the agglomerating anode composition typically had and is lower than 0.5% porosity under described these conditions.

Can sintered anode be linked to each other with suitable conductive support in the electrolytic etching of metal preparation vessel by for example welding, diffusion welding, brazing, mechanical fixation, bonding etc.For example, noble electrode can comprise foregoing sintering metal, and described sintering metal is contacted in proper order and is connected in the higher zone of transition of metal content and metal or metal alloy end such as nickel or Inconel(nickel alloys) (Inconet).Nickel or nichrome rod can be welded to described metal end.Described zone of transition for example can comprise that 4 have the layer that gradient is formed, and wherein, the layer of 25 weight %Ni is adjacent with the sintering metal end, is 50,70 and 100 weight %Ni afterwards, and the remaining part of composition then is the mixture of aforesaid oxide compound and metal-powder.

We have prepared several cermet inert anode compositions according to abovementioned steps, and their diameter is about 5/8 inch or about 2 inches, about 5 inches of length.With similar Hall-Heroult Thoughs shown in Figure 1 in these compositions are estimated.This Thoughs was worked 100 hours down at 960 ℃, and wherein, aluminum fluoride is about 1: 1 with the ratio of Sodium Fluoride saline solution, and alumina concentration is maintained at about 7-7.5 weight %.Anode composition and adopt the foreign matter content in the aluminium of described Thoughs preparation in table 7, to provide.The average result of foreign matter content representative four specimen after 100 hours test shown in the table 7, these four specimen are taken from four different sites on the prepared metal respectively.Foreign matter content in the intermediate stage sample of prepared aluminium is lower than listed final impurity level all the time.

Table 7

Sample number into spectrum	Form	Porosity	?Fe	?Cu	?Ni
						????1	?3Ag-14Cu-42.9NiO-40.1Fe 2O 3		?0.191	?0.024	?0.044
????2	?3Ag-14Cu-42.9NiO-40.1Fe 2O 3		?0.26	?0.012	?0.022
						????3	?3Ag-14Cu-26.45NiO-56.55Fe 2O 3		?0.375	?0.13	?0.1
????4	?3Ag-14Cu-42.9NiO-40.1Fe 2O 3		?0.49	?0.05	?0.085
						????5	?3Ag-14Cu-42.9NiO-40.1Fe 2O 3		?0.36	?0.034	?0.027
????6	?5Ag-10Cu-43.95NiO-41.05Fe 2O 3		?0.4	?0.06	?0.19
						????7	?3Ag-14Cu-42.9NiO-40.1Fe 2O 3		?0.38	?0.095	?0.12
????8	?2Ag-15Cu-42.9NiO-40.1Fe 2O 3		?0.5	?0.13	?0.33
						????9	?2Ag-15Cu-42.9NiO-40.1Fe 2O 3		?0.1	?0.16	?0.26
????10	?3Ag-11Cu-44.46NiO-41.54Fe 2O 3		?0.14	?0.017	?0.13
						????11	?1Ag-14Cu-27.75NiO-57.25Fe 2O 3		?0.24	?0.1	?0.143
????12	?1Ag-14Cu-27.96NiO-57.04Fe 2O 3	?0.127	?0.07	?0.011	?0.0212
						????13	?1Ag-14Cu-27.96NiO-57.04Fe 2O 3	?0.168	?0.22	?0.04	?0.09
????14	?1Ag-14Cu-27.96NiO-57.04Fe 2O 3	?0.180	?0.1	?0.03	?0.05
						????15	?1Ag-14Cu-27.96NiO-57.04Fe 2O 3	?0.175	?0.12	?0.04	?0.06
????16	?1Ag-14Cu-27.96NiO-57.04Fe 2O 3	?0.203	?0.08	?0.02	?0.1
						????17	?1Ag-14Cu-27.96NiO-57.04Fe 2O 3	?0.230	?0.12	?0.01	?0.04
????18	?1Ag-14Cu-27.96NiO-57.04Fe 2O 3	?0.184	?0.17	?0.18	?0.47

Sample number into spectrum	Form	Porosity	?Fe	?Cu		?Ni
							????19	?1Ag-14Cu-27.96NiO-57.04Fe 2O 3	?0.193	?0.29	?0.044		?0.44
????20	?1Ag-14Cu-5ZnO-28.08NiO-56.92Fe 2O 3	?0.201	?0.16	?0.02		?0.02
							????21	?1Ag-14Cu-27.96NiO-57.04Fe 2O 3	?0.144	?0.44	?0.092		?0.15
????22	?1Ag-14Cu-5ZnO-28.08NiO-56.92Fe 2O 3	?0.191	?0.48	?0.046		?0.17
							????23	?1Ag-14Cu-5ZnO-28.08NiO-56.92Fe 2O 3	?0.214	?0.185	?0.04		?0.047
????24	?1Ag-14Cu-27.96NiO-57.04Fe 2O 3	?0.201	?0.15	?0.06		?0.123
							????25	?1Ag-14Cu-5ZnO-28.08NiO-56.92Fe 2O 3	?0.208	?0.22	?0.05		?0.08
????26	?1Ag-14Cu-27.96NiO-57.04Fe 2O 3	?0.201	?0.18	?0.03		?0.08
							????27	?1Ag-14Cu-5ZnO-28.08NiO-56.92Fe 2O 3	?0.252	?0.21	?0.05		?0.08
????28	?1Ag-14Cu-27.96NiO-57.04Fe 2O 3	?0.203	?0.21	?0.057		?0.123
							????29	?1Ag-14Cu-27.35NiO-55.95Fe 2O 3-1.7ZnO	?0.251	?0.12	?0.03		?0.043
????30	?1Ag-14Cu-27.96NiO-57.04Fe 2O 3	?0.238	?0.12	?0.05		?0.184
							????31	?1Ag-14Cu-27.96NiO-57.04Fe 2O 3	?0.221	?0.185	?0.048		?0.157
????32	?1Ag-14Cu-27.35NiO-55.95Fe 2O 3-1.7ZnO	?0.256	?0.16	?0.019		?0.028
							????33	?1Pd-15Cu-40.48Fe 2O 3-43.32NiO-0.2ZnO	?0.149	?0.11	?0.01		?0.024
????34	?1Ag-14Cu-27.96NiO-57.04Fe 2O 3	?0.241	?0.186	?0.05		?0.22
							????35	?3Pd-14Cu-42.91NiO-40.09Fe 2O 3	?0.107	?0.2	?0.02		?0.11
????36	?1Pt-15Cu-57.12Fe 2O 3-26.88NiO	?0.105	?0.14	?0.024		?0.041
							????37	?1Pd-15Cu-57Fe 2O 3-27.8NiO-0.2ZnO	?0.279	?0.115	?0.014		?0.023

Sample number into spectrum	Form	Porosity	?Fe	?Cu	?Ni
						????38	?1Pd-15Cu-40.48Fe 2O 3-43.32NiO-0.2ZnO	?0.191	?0.116	?0.031	?0.038
????39	?1Pd-15Cu-40.48Fe 2O 3-43.32NiO-0.2ZnO	?0.253	?0.115	?0.07	?0.085
						????40	?0.5Pd-16Cu-43.27NiO-40.43Fe 2O 3-0.2ZnO	?0.129	?0.096	?0.042	?0.06
????41	?0.5Pd-16Cu-43.27NiO-40.43Fe 2O 3-0.2ZnO	?0.137	?0.113	?0.033	?0.084
						????42	?0.1Pd-0.9Ag-15Cu-43.32NiO-40.48Fe 2O 3-0.2ZnO		?0.18	?0.04	?0.066
????43	?0.05Pd-0.95Ag-14Cu-27.9NiO-56.9Fe 2O 3-0.2ZnO	?0.184	?0.038	?0.013	?0.025
						????44	?0.1Pd-0.9Ag-14Cu-27.9NiO-56.9Fe 2O 3-0.2ZnO	?0.148	?0.18	?0.025	?0.05
????45	?0.1Pd-0.9Ag-14Cu-27.35NiO-55.95Fe 2O 3-1.7ZnO	?0.142	?0.09	?0.02	?0.03
						????46	?0.05Pd-0.95Ag-14Cu-27.35NiO-55.95Fe 2O 3-1.7ZnO	?0.160	?0.35	?0.052	?0.084
????47	?1Ru-14Cu-27.35NiO-55.95Fe 2O 3-1.7ZnO	?0.215	?0.27	?0.047	?0.081
						????48	?0.1Pd-0.9Ag-14Cu-55.81Fe 2O 3-27.49NiO-1.7ZnO	?0.222	?0.31	?0.096	?0.18
????49	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO	?0.147	?0.15	?0.008	?0.027
						????50	?0.1Pd-2.7Ag(asAg 2O)-14.02Cu-26.9NiO-54.6Fe 2O 3-1.66ZnO	?0.180	?0.17	?0.03	?0.049
????51	?0.1Pd-0.9Ag(asAg 2O)-14Cu-25.49NiO-55.81Fe 2O 3-1.7ZnO	?0.203	?0.2	?0.05	?0.03
						????52	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO	?0.279	?0.27	?0.06	?0.36
????53	?0.1Pd-0.9Ag(asAg 2O)-14Cu-25.49NiO-55.81Fe 2O 3-1.7ZnO	?0.179	?0.07	?0.023	?0.02
						????54	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO	?0.321	?0.15	?0.05	?0.028
????55	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO	?0.212	?0.19	?0.02	?0.075
						????56	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO	?0.194	?0.13	?0.01	?0.02

" as " expression " its form is " in the table.

Sample number into spectrum	Form	Porosity	?Fe	?Cu	?Ni
						????57	?1.0Ag(asAg 2O)-14Cu(as?CuO)-27.5NiO-55.8Fe 2O 3-1.7ZnO	?0.202	?0.12	?0.023	?0.03
????58	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO	?0.241	?0.10	?0.01	?0.02
						????59	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO		?0.070	?0.005	?0.007
????60	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO		?0.054	?0.005	?0.008
						????61	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO		?0.191	?0.05	?0.060
????62	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO		?0.120	?0.016	?0.030
						????63	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO		?0.110	?0.011	?0.033
????64	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO		?0.221	?0.039	?0.080
						????65	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO		?0.131	?0.015	?0.032
????66	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO		?0.089	?0.006	?0.014
						????67	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO *-55.23Fe 2O 3-1.68ZnO		?0.100	?0.017	?0.014
????68	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO *-55.23Fe 2O 3-1.68ZnO		?0.141	?0.036	?0.057
						????69	?1.86Ag(asAg 2O)-7.01Cu(as?CuO)-7.01Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO		?0.830	?0.019	?0.017
????70	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO *-55.23Fe 2O 3-1.68ZnO		?0.075	?0.014	?0.025
						????71	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO *-55.23Fe 2O 3-1.68ZnO		?0.067	?0.012	?0.033
????72	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO		?0.073	?0.007	?0.017
						????73	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO		?0.121	?0.038	?0.071
????74	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO *-55.23Fe 2O 3-1.68ZnO		?0.086	?0.016	?0.028
						????75	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO *-55.23Fe 2O 3-1.68ZnO		?0.094	?0.043	?0.060

" as " expression " its form is " in the table.

Sample number into spectrum	Form	Porosity	?Fe	?Cu	?Ni
						????76	?1.86Ag(asAg 2O)-7.01Cu(as?CuO)-7.01-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO		?0.063	?0.044	?0.027
????77	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO		?0.101	?0.019	?0.032
						????78	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO		?0.085	?0.017	?0.027
????79	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO		?0.089	?0.026	?0.051
						????80	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO		?0.071	?0.016	?0.027
????81	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO		?0.086	?0.044	?0.058
						????82	?1.86Ag(asAg 2O)-7.01Cu(as?CuO)-7.01-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO		?0.064	?0.040	?0.016
????83	?1.86Ag(asAg 2O)-7.01Cu(as?CuO)-7.01-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO		?0.084	?0.116	?0.172
						????84	?1.86Ag(asAg 2O)-3.52Cu(as?CuO)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO		?0.063	?0.027	?0.028
????85	?1.86Ag(asAg 2O)-3.52Cu(as?CuO)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO		?0.223	?0.094	?0.122
						????86	?1.86Ag(asAg 2O)-3.52Cu(as?CuO)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO		?0.150	?0.031	?0.042
????87	?1.86Ag(asAg 2O)-3.52Cu(as?CuO)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO		?0.090	?0.022	?0.025
						????88	?1.86Ag(asAg 2O)-3.52Cu(as?CuO)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO		?0.068	?0.023	?0.029
????89	?1.86Ag(asAg 2O)-3.52Cu(as?CuO)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO		?0.216	?0.545	?0.089
						????90	?1.86Ag(asAg 2O)-3.52Cu(as?CuO)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO		?0.213	?0.122	?0.168
????91	?1.86Ag(asAg 2O)-3.52Cu(as?CuO)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO		?0.064	?0.023	?0.018
						????92	?1.86Ag(asAg 2O)-3.52Cu(as?CuO)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO		?0.082	?0.033	?0.033
????93	?1.86Ag(asAg 2O)-3.52Cu(as?CuO)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO		?0.173	?0.112	?0.122
						????94	?1.86Ag(asAg 2O)-3.52Cu(as?CuO)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO		?0.132	?0.052	?0.070

" as " expression " its form is " in the table.

Sample number into spectrum	Form	Porosity		?Fe		?Cu	?Ni
								????95	?1.86Ag(asAg 2O)-3.52Cu(as?CuO)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO			?0.142		?0.098	?0.089
????96	?1.86Ag(asAg 2O)-3.52Cu(as?CuO)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO			?0.100		?0.023	?0.017
								????97	?1.86Ag(asAg 2O)-3.52Cu(as?CuO)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO			?0.072		?0.021	?0.019
????98	?1.86Ag(asAg 2O)-3.52Cu(as?CuO)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO			?0.198		?0.021	?0.117
								????99	?1.86Ag(asAg 2O)-3.52Cu(as?CuO)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO			?0.092		?0.065	?0.065
????100	?1.86Ag(asAg 2O)-3.52Cu(as?CuO)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO			?0.131		?0.044	?0.045
								????101	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO			?0.288		?0.031	?0.124
????102	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO			?0.104		?0.033	?0.037
								????103	?1.86Ag(asAg 2O)-3.52Cu(as?CuO)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO			?0.092		?0.019	?0.030
????104	?1.86Ag(asAg 2O)-3.52Cu(asCuO)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO			?0.121		?0.048	?0.057
								????105	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO			?0.121		?0.021	?0.035
????106	?1.86Ag(asAg 2O)-3.52Cu(as?Cu 2O)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO			?0.151		?0.056	?0.082
								????107	?1.86Ag(asAg 2O)-7.01Cu(as?Cu 2O)-7.01-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO			?0.253		?0.081	?0.092
????108	?1.86Ag(asAg 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO			?0.071		?0.035	?0.032
								????109	?1.86Ag(asAg 2O)-3.52Cu(as?Cu 2O)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO			?0.071		?0.035	?0.032
????110	?1.86Ag(asAg 2O)-3.52Cu(as?Cu 2O)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO			?0.131		?0.045	?0.039
								????111	?1.86Ag(asAg 2O)-3.52Cu(as?Cu 2O)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO			?0.233		?0.060	?0.089
????112	?1.86Ag(asAg 2O)-3.52Cu(as?Cu 2O)-10.5-Cu-27.2NiO-55.24Fe 2O 3-1.68ZnO			?0.111		?0.036	?0.365
								????113	?1.86Ag(as?Ag 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO			?0.264		?0.193	?0.284
????114	?1.86Ag(as?Ag 2O)-14.02Cu-27.21NiO-55.23Fe 2O 3-1.68ZnO			?0.055		?0.007	?0.016

" as " expression " its form is " in the table.

Result in the table 7 shows: adopt described cermet inert anode, the pollution level of aluminium is very low, and in addition, for the sample of each test, the wear rate of inert anode is extremely low.The operation of optimization process parameter and electrolyzer can further improve the purity according to the aluminium of this courage preparation.

Inert anode prepares aluminium for being used to of working under about 800-1000 ℃ temperature electrolyzer is particularly useful.Particularly preferred electrolyzer is worked under preferably about 930-970 ℃ temperature at about 900-980 ℃.Electric current flows through between inert anode and negative electrode by the melting salt body lotion that comprises ionogen and wait to collect the oxide compound of metal.At an electrolyzer that preferably is used for preparing aluminium, described ionogen comprises aluminum fluoride and Sodium Fluoride, and described metal oxide is an aluminum oxide, and the weight ratio of Sodium Fluoride and aluminum fluoride is about 0.7-1.25, preferably about 1.0-1.20.Described ionogen can also contain Calcium Fluoride (Fluorspan), lithium fluoride and/or magnesium fluoride.

Invention has been described though adopt preferred embodiment,, only otherwise depart from regulation scope of the present invention in the claim of back, can carry out various changes to the present invention, add and revise.

Claims (89)

1. cermet inert anode composition that is used for the fused salt body lotion, it comprises:

A kind of formula is Ni _xFe _2yM _zO _{(3y+x+z) ± δ}Ceramic phase, wherein, M is at least a Zn of being selected from, Co, Al, Li, Cu, Ti, V, Cr, Zr, Nb, Ta, W, Mb, the metal of Hf and rare earth, the about 0.1-0.99 of X, the about 0.0001-0.9 of y, the about 0.0001-0.5 of Z, S are 0-0.3; And

A kind of metallographic phase.

2. according to the cermet inert anode composition of claim 1, wherein, described ceramic phase is about described ceramic-metallic 50-95 weight %, and described metallographic phase is about described ceramic-metallic 5-50 weight %.

3. according to the cermet inert anode composition of claim 1, wherein, described ceramic phase is about described ceramic-metallic 80-90 weight %, and described metallographic phase is about described ceramic-metallic 10-20 weight %.

4. according to the cermet inert anode composition of claim 1, wherein, M is Zn, Co, Cr and/or Al.

5. according to the cermet inert anode composition of claim 1, wherein, M comprises Zn.

6. according to the cermet inert anode composition of claim 5, wherein, the about 0.2-0.99 of X, the about 0.0001-0.8 of y, the about 0.0001-0.3 of Z.

7. according to the cermet inert anode composition of claim 5, wherein, the about 0.45-0.8 of X, the about 0.05-0.499 of y, the about 0.001-0.26 of Z.

8. according to the cermet inert anode composition of claim 1, wherein, the about 0.45-0.65 of X, the about 0.2-0.49 of y, the about 0.001-0.22 of Z.

9. according to the cermet inert anode composition of claim 1, wherein, the about 0.05-0.30 of Z.

10. according to the cermet inert anode composition of claim 5, wherein, described ceramic phase has the Hall groove electrolytic solution solubleness that total dissolved oxygen thing amount is lower than 0.1 weight %.

11. according to the cermet inert anode composition of claim 5, wherein, described ceramic phase has the Hall groove electrolytic solution solubleness that total dissolved oxygen thing amount is lower than 0.08 weight %.

12. according to the cermet inert anode composition of claim 5, wherein, described ceramic phase has the Hall groove electrolytic solution solubleness that total dissolved oxygen thing amount is lower than 0.075 weight %.

13. according to the cermet inert anode composition of claim 5, wherein, described ceramic phase has the Hall groove electrolytic solution solubleness that is lower than 0.03 weight %NiO.

14. according to the cermet inert anode composition of claim 5, wherein, described ceramic phase has the Hall groove electrolytic solution solubleness that is lower than 0.025 weight %NiO.

15. according to the cermet inert anode composition of claim 1, wherein, M comprises Co.

16. according to the cermet inert anode composition of claim 15, wherein, the about 0.15-0.99 of X, the about 0.0001-0.85 of y, the about 0.0001-0.45 of Z.

17. according to the cermet inert anode composition of claim 15, wherein, the about 0.15-0.6 of X, the about 0.4-0.6 of y, the about 0.001-0.25 of Z.

18. according to the cermet inert anode composition of claim 15, wherein, the about 0.25-0.55 of X, the about 0.45-0.55 of y, the about 0.001-0.2 of Z.

19. according to the cermet inert anode composition of claim 15, wherein, X is about 0.35, y is about 0.5, and Z about 0.15.

20. according to the cermet inert anode composition of claim 15, wherein, described ceramic phase has the Hall groove electrolytic solution solubleness that total dissolved oxygen thing amount is lower than 0.1 weight %.

21. according to the cermet inert anode composition of claim 15, wherein, described ceramic phase has the Hall groove electrolytic solution solubleness that total dissolved oxygen thing amount is lower than 0.08 weight %.

22. according to the cermet inert anode composition of claim 1, wherein, described metallographic phase comprises at least a Cu of being selected from, Ag, Pd, Pt, Au, Rh, Ru, the metal of Ir and Os.

23. according to the cermet inert anode composition of claim 22, wherein, described metallographic phase is basically by Cu, Ag, Pd, the constituting of Pt or they.

24. according to the cermet inert anode composition of claim 1, wherein, described metallographic phase comprises the matrix metal of at least a Cu of being selected from and Ag, and at least a Ag that is selected from, Pd, Pt, Au, Rh, Ru, the inert metal of Ir and Os.

25. according to the cermet inert anode composition of claim 24, wherein, described matrix metal comprises Cu, described at least a inert metal comprises Ag, Pd, Pt, Au, Rh or their combination.

26. according to the cermet inert anode composition of claim 25, wherein said at least a inert metal comprises Ag.

27. according to the cermet inert anode composition of claim 26, wherein, Ag accounts for below the 15 weight % of described metallographic phase.

28. according to the cermet inert anode composition of claim 26, wherein, Ag accounts for below the 10 weight % of described metallographic phase.

29. according to the cermet inert anode composition of claim 26, wherein, Ag accounts for the 0.2-9 weight % of described metallographic phase.

30. according to the cermet inert anode composition of claim 26, wherein, the fusing point of described metallographic phase is higher than 800 ℃.

31. according to the cermet inert anode composition of claim 25, wherein, described at least a inert metal comprises Pd.

32. according to the cermet inert anode composition of claim 31, wherein, Pd accounts for below the 20 weight % of described metallographic phase.

33. according to the cermet inert anode composition of claim 31, wherein, Pd accounts for the 0.1-10 weight % of described metallographic phase.

34. according to the cermet inert anode composition of claim 25, wherein, described at least a inert metal comprises Ag and Pd.

35. according to the cermet inert anode composition of claim 34, wherein, Ag is about the 0.5-30 weight % of described metallographic phase, Pd is about the 0.01-10 weight % of described metallographic phase.

36. according to the cermet inert anode composition of claim 24, wherein, described matrix metal comprises Ag, described at least a inert metal comprises Pd, Pt, Au, Rh or their combination.

37. according to the cermet inert anode composition of claim 36, wherein, described inert metal comprises Pd.

38. according to the cermet inert anode composition of claim 1, wherein, the fusing point of described metallographic phase is higher than about 800 ℃.

39. according to the cermet inert anode composition of claim 1, wherein, the fusing point of described metallographic phase is higher than about 900 ℃.

40. according to the cermet inert anode composition of claim 1, wherein, the fusing point of described metallographic phase is higher than about 1000 ℃.

41. according to the cermet inert anode composition of claim 1, wherein, M comprises Zn and/or Co, described metallographic phase comprises at least a Cu of being selected from, Ag, Pd, Pt, Au, Rh, Ru, the metal of Ir and Os.

42. according to the cermet inert anode composition of claim 41, wherein, described metallographic phase comprises Cu and Ag.

43. according to the cermet inert anode composition of claim 42, wherein, M comprises Zn.

44. according to the cermet inert anode composition of claim 43, wherein, the about 0.45-0.8 of X, the about 0.05-0.499 of y, the about 0.001-0.26 of Z.

45. according to the cermet inert anode composition of claim 43, wherein, the about 0.45-0.65 of X, the about 0.2-0.49 of y, the about 0.001-0.22 of Z.

46. according to the cermet inert anode composition of claim 43, wherein, the about 0.05-0.30 of Z.

47. cermet inert anode preparation of compositions method, described method comprises:

With a kind of metal and formula is Ni _xFe _2yM _zO _{(3y+x+z) ± δ}Stupalith mix, wherein, M is at least a Zn of being selected from, Co, Al, Li, Cu, Ti, V, Cr, Zr, Nb, Ta, W, Mb, the metal of Hf and rare earth, the about 0.1-0.99 of X, the about 0.0001-0.9 of y, the about 0.0001-0.5 of Z, δ are 0-0.3;

Suppress described metal and ceramic mixture; And

Described mixture is carried out sintering, comprise the cermet inert anode composition of a kind of metallographic phase and a kind of ceramic phase with formation.

48. according to the method for claim 47, wherein, M is Zn, Cr and/or Al.

49. according to the method for claim 47, wherein, described metallographic phase comprises at least a Cu of being selected from, Ag, Pd, Pt, Au, Rh, Ru, the metal of Ir and Os.

50. according to the method for claim 47, wherein, described metallographic phase comprises the matrix metal of at least a Cu of being selected from and Ag, and at least a Ag that is selected from, Pd, Pt, Au, Rh, Ru, the inert metal of Ir or Os.

51. according to the method for claim 50, wherein, described matrix metal comprises Cu, described at least a inert metal comprises Ag, Pd, Pt, Au, Rh or their combination.

52. according to the method for claim 51, wherein, described at least a inert metal comprises Ag.

53. according to the method for claim 47, wherein, M comprises Zn and/or Co, described metallographic phase comprises at least a Cu of being selected from, Ag, Pd, Pt, Au, Rh, Ru, the metal of Ir and Os.

54. according to the method for claim 53, wherein, described metallographic phase comprises Cu and Ag.

55. according to the method for claim 54, wherein, M comprises Zn.

56. according to the method for claim 55, wherein, the about 0.45-0.8 of X, the about 0.05-0.499 of y, the about 0.001-0.26 of Z.

57. according to the method for claim 55, wherein, the about 0.45-0.65 of X, the about 0.2-0.49 of y, the about 0.001-0.22 of Z.

58. according to the method for claim 55, wherein, the about 0.05-0.30 of Z.

59. according to the method for claim 47, wherein, described metallographic phase to small part is that the oxide compound by this metal provides.

60. according to the method for claim 59, wherein, the argentiferous oxide compound of oxide compound bag of described metal.

61. according to the method for claim 59, wherein, the copper bearing oxide compound of oxide compound bag of described metal.

62. be used to prepare the electrolyzer of metal, it comprises:

Comprise ionogen and waiting and collect the fused salt body lotion of the oxide compound of metal;

Negative electrode; And

Comprising metallographic phase and formula is Ni _xFe _2yM _zO _{(3y+x+z) ± δ}The cermet inert anode of ceramic phase, wherein, M is at least a Zn of being selected from, Co, Al, Li, Cu, Ti, V, Cr, Zr, Nb, Ta, W, Mb, the metal of Hf and rare earth, the about 0.1-0.99 of X, the about 0.0001-0.9 of y, the about 0.0001-0.5 of Z, δ are 0-0.3.

63. according to the method for claim 59, wherein, M is Zn, Cr and/or Al.

64. according to the method for claim 62, wherein, described metallographic phase comprises at least a Cu of being selected from, Ag, Pd, Pt, Au, Rh, Ru, the metal of Ir and Os.

65. according to the method for claim 62, wherein, described metallographic phase comprises the matrix metal of at least a Cu of being selected from and Ag, and at least a Ag that is selected from, Pd, Pt, Au, Rh, Ru, the inert metal of Ir and Os.

66. according to the method for claim 65, wherein, described matrix metal comprises Cu, described at least a inert metal comprises Ag, Pd, Pt, Au, Rh or their combination.

67. according to the method for claim 66, wherein, described at least a inert metal comprises Ag.

68. according to the method for claim 62, wherein, M comprises Zn and/or Co, described metallographic phase comprises at least a Cu of being selected from, Ag, Pd, Pt, Au, Rh, Ru, the inert metal of Ir and Os.

69. according to the method for claim 65, wherein, described metallographic phase comprises Cu and Ag.

70. according to the method for claim 69, wherein, M comprises Zn.

71. according to the method for claim 70, the about 0.45-0.8 of X wherein, the about 0.05-0.499 of y, the about 0.001-0.26 of Z.

72. according to the method for claim 70, the about 0.45-0.65 of X wherein, the about 0.2-0.49 of y, the about 0.001-0.22 of Z.

73. according to the method for claim 70, the about 0.05-0.30 of Z wherein.

74. the preparation method of technical grade fine aluminium comprises: the electrolytic solution of the oxide compound of electric current by comprising ionogen and aluminium is flow through between cermet inert anode and negative electrode; And

Aluminium is reclaimed, and described aluminium contains 0.20 weight %Fe at most, 0.1 weight %Cu and 0.034 weight %Ni, and wherein, described cermet inert anode comprises metallographic phase and formula is Ni _xFe _2yM _zO _{(3y+x+z) ± δ}Ceramic phase, wherein, M is at least a Zn of being selected from, Co, Al, Li, Cu, Ti, V, Cr, Zr, Nb, Ta, W, Mb, the metal of Hf and rare earth, the about 0.1-0.99 of X, the about 0.0001-0.9 of y, the about 0.0001-0.5 of Z, δ are 0-0.3.

75. according to the method for claim 74, wherein, the aluminium that is reclaimed comprises 0.15 weight %Fe at most, 0.034 weight %Cu and 0.03 weight %Ni.

76. according to the method for claim 74, wherein, comprise 0.13 weight %Fe in the aluminium that is reclaimed at most, 0.03 weight %Cu and 0.03 weight %Ni.

77. according to the method for claim 74, wherein, the aluminium that is reclaimed also comprises maximum 0.2 weight %Si, 0.03 weight %Zn and 0.03 weight %Co.

78. according to the method for claim 74, wherein, the total amount of the Cu that the aluminium that is reclaimed contains at most, Ni and Co is 0.10 weight %.

79. according to the method for claim 74, wherein, M is Zn, Cr and/or Al.

80. according to the method for claim 74, wherein said metallographic phase comprises at least a Cu of being selected from, Ag, Pd, Pt, Au, Rh, Ru, the metal of Ir and Os.

81. according to the method for claim 74, wherein, described metallographic phase comprises the matrix metal of at least a Cu of being selected from and Ag, and at least a Ag that is selected from, Pd, Pt, Au, Rh, Ru, the inert metal of Ir and Os.

82. 1 method according to Claim 8, wherein, described matrix metal comprises Cu, and described at least a inert metal comprises Ag, Pd, Pt, Au, Rh or their combination.

83. 2 method according to Claim 8, wherein, described at least a inert metal comprises Ag.

84. according to the method for claim 74, wherein, M comprises Zn and/or Co, described metallographic phase comprises at least a Cu of being selected from, Ag, Pd, Pt, Au, Rh, Ru, the metal of Ir and Os.

85. 4 method according to Claim 8, wherein said metallographic phase comprises Cu and Ag.

86. 5 method according to Claim 8, wherein, M comprises Zn.

87. 6 method according to Claim 8, wherein, the about 0.45-0.8 of X, the about 0.05-0.499 of y, the about 0.001-0.26 of Z.

88. 6 method according to Claim 8, wherein, the about 0.45-0.65 of X, the about 0.2-0.49 of y, the about 0.001-0.22 of Z.

89. 6 method according to Claim 8, wherein, the about 0.05-0.30 of Z.

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